Catalyst carrier for maximizing light naphtha and heavy naphtha in hydrocracking and method for preparing the same

Abstract

The application discloses a catalyst carrier for hydrocracking and producing light naphtha and heavy naphtha and a preparation method thereof, and the catalyst carrier contains Y / La2O3 / PMo heteropolyacid / KIT-6 mesoporous composite oxides. The preparation method improves the mesopore size distribution, improves the selective cracking performance of distillate oil, and improves the yield of light naphtha and heavy naphtha. The preparation method improves the selective cracking performance of the carrier for distillate oil, and improves the yield of light naphtha and heavy naphtha.

Description

TECHNICAL FIELD

[0001] The application relates to a catalyst carrier for hydrocracking to produce light naphtha and heavy naphtha and a preparation method thereof, and belongs to the technical field of carrier materials. BACKGROUND

[0002] Molecular sieves are widely used in adsorption, separation, catalysis and other fields due to their unique pore structure, especially in petroleum and chemical industry. With the continuous development of molecular sieve catalytic applications, single-pore molecular sieves cannot meet the diverse needs of catalyst preparation. Microporous molecular sieves are mainly characterized by strong acidity and high structural stability in heterogeneous catalysis applications. However, due to the small pore size and long and narrow pore channel of microporous molecular sieves, it is difficult for large molecules in heavy oil to diffuse into the pore channel, which reduces the utilization rate of acid sites inside the microporous molecular sieve channel. In addition, the narrow and long pore channel has a large diffusion resistance, which affects the rapid diffusion of reaction product molecules, and easily leads to deep cracking and coking. Mesoporous molecular sieves can make up for the limitations of microporous molecular sieves in internal diffusion of reactants and reaction products, but the structural stability of mesoporous molecular sieves is often poor, which also limits their catalytic applications. Micro-mesoporous composite molecular sieve materials can produce good synergistic effect and catalytic performance by taking the advantages of several single materials, and the comprehensive performance is better than that of the original component materials. This kind of molecular sieve with multiple structures and superimposed functions can avoid the defects of single pore structure, and the multi-level pore system can provide different size channels, which will be very helpful to solve the problem of mass transfer of large molecules.

[0003] Chinese patent CN111484037A discloses a method for synthesizing SSZ-13 molecular sieves with different silicon-aluminum ratios by Y molecular sieve crystal transformation. TMADaOH is used as a structure directing agent, and an alkali source, a silicon source, a structure directing agent, a mesoporous template agent and water are uniformly mixed to prepare a sol, an aluminum source with different contents is added to obtain an initial gel, a hydrothermal crystallization reaction is carried out, and a crystallization reaction product is obtained after the reaction is completed. After cooling and washing to neutral, drying obtains a molecular sieve raw powder, and then the molecular sieve raw powder is calcined to obtain SSZ-13 molecular sieves with different silicon-aluminum ratios. However, the SSZ-13 molecular sieves obtained by the method have relatively low pore size and pore volume, and La2O3 / PMo heteropoly acid / KIT-6 molecular sieves are not involved.

[0004] Chinese patent CN110357121A discloses a preparation method of small crystal grain nano multi-level hole SSZ-13 molecular sieve, which is prepared by using TMADaOH as a structure directing agent and TPOAC as a mesoporous template agent, mixing an alkali source, a silicon source, a structure directing agent, a mesoporous template agent and water uniformly, adding or not adding an aluminum source to prepare a sol, adding a Y type molecular sieve to obtain an initial gel, and performing a hydrothermal crystallization reaction, and then calcining a reaction product to obtain the small crystal grain nano multi-level hole SSZ-13 molecular sieve. However, the technology only synthesizes the SSZ-13 molecular sieve, and does not involve the La2O3 / PMo heteropoly acid / KIT-6 molecular sieve, and the function of the molecular sieve is limited.

[0005] Chinese patent CN114130427A discloses a Y / SSZ-13 / rare earth / ASA composite material, a hydrocracking catalyst, a catalyst carrier and a preparation method thereof, which comprises the following steps: step 1, mixing Y molecular sieve, SSZ-13 molecular sieve, an aluminum source, an alkaline compound and water, and heating and stirring; step 2, adding a silicon source and a rare earth precursor into the mixture in step 1, and heating and stirring to obtain the Y / SSZ-13 / rare earth / ASA composite material. However, the technology only synthesizes the Y / SSZ-13 / rare earth / ASA composite material, and does not involve the La2O3 / PMo heteropoly acid / KIT-6 molecular sieve, and the function of the molecular sieve is limited.

[0006] Chinese patent CN106311319A discloses a hydrocracking catalyst containing micro-mesoporous composite molecular sieve and application thereof. The catalyst comprises a catalyst carrier and an active component. The catalyst carrier comprises 5-50wt% of micro-mesoporous composite molecular sieve, 5-30wt% of Y microporous molecular sieve, 10-50wt% of alumina, 20-55wt% of amorphous silica-alumina, 5-25wt% of binder and 1-5wt% of extrusion aid, according to the weight percentage of the catalyst carrier. The active component comprises 10%-40% of VIB group metal oxide, 1%-20% of VIII group metal oxide and / or 0.1%-10% of VA group oxide, according to the weight percentage of the catalyst carrier. However, the catalyst contains 5-50wt% of micro-mesoporous composite molecular sieve, and the molecular sieve composition is Beta / KIT-6 composite molecular sieve. The Beta molecular sieve is a microporous molecular sieve for isomerization, and has a performance worse than the Y molecular sieve in terms of pore size and acid strength. The KIT-6 mesoporous molecular sieve is a full-silicon molecular sieve, and has no acidity without modification. Therefore, the Beta / KIT-6 micro-mesoporous composite molecular sieve used in the technology has a weaker mesoporous composite oxide than the Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve of the present application in terms of acid strength, resulting in a relatively low cracking activity, and thus a lower yield of light naphtha and heavy naphtha. SUMMARY

[0007] The present application aims to provide a catalyst carrier for hydrocracking to produce more light naphtha and heavy naphtha and a preparation method thereof, so as to solve the problems of low cracking selectivity of existing catalysts for distillate oil and low yield of light naphtha and heavy naphtha in hydrocracking products.

[0008] To achieve the above-mentioned purpose, the present application provides a preparation method of a catalyst carrier for hydrocracking to produce more light naphtha and heavy naphtha, the catalyst carrier containing Y / La2O3 / PMo heteropoly acid / KIT-6 mesoporous composite oxide, the preparation method comprising the following steps:

[0009] (1) spray adsorbing KIT-6 molecular sieve with a phosphomolybdic acid heteropoly complex aqueous solution containing lanthanum nitrate, drying and calcining to obtain La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide;

[0010] (2) adding La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide obtained in step (1), Y molecular sieve directing agent, aluminum sulfate solution, sodium metaaluminate solution B and organic matter to a water glass solution, stirring uniformly, then adding deionized water, mixing uniformly, crystallizing to obtain a slurry of Y / La2O3 / PMo heteropoly acid / KIT-6 mesoporous composite oxide, wherein the mass ratio of La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide:Y molecular sieve directing agent:Al2O3:Na2O:SiO2:organic matter:H2O is = (0.8-1.5):(0.09-0.15):1:(0.08-0.96):(2.4-3.2):(0.3-0.7):(13-41); after solid-liquid separation, Y / La2O3 / PMo heteropoly acid / KIT-6 mesoporous composite oxide is obtained;

[0011] (3) treating Y / La2O3 / PMo heteropoly acid / KIT-6 mesoporous composite oxide under the condition of water vapor;

[0012] (4) treating Y / La2O3 / PMo heteropoly acid / KIT-6 mesoporous composite oxide after water vapor treatment in a mixed solution of ammonium sulfate and citric acid to obtain a slurry;

[0013] (5) adding amorphous phosphorus aluminum, phosphomolybdic acid heteropoly and macroporous aluminum oxide binder to the slurry in step (4), and then mixing, rolling, and extruding to obtain a catalyst carrier containing Y / La2O3 / PMo heteropoly acid / KIT-6 mesoporous composite oxide.

[0014] The preparation method of the application, in step (1), the mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic acid heteropoly acid: aqueous solution is 1: (0.01-0.12): (0.1-0.25): (0.5-2).

[0015] The preparation method of the application, preferably, in step (1), the mass ratio of KIT-6 molecular sieve: lanthanum nitrate: Pmo heteropoly acid: aqueous solution is 1: (0.05-0.1): (0.15-0.2): (0.5-2).

[0016] The preparation method of the application, in step (1), the drying temperature is 80-100℃; the calcination temperature is 300-400℃.

[0017] The preparation method of the application, in step (2), the preparation method of the Y molecular sieve directing agent comprises: adding sodium metaaluminate solution A and water glass solution into deionized water, aging to obtain the Y molecular sieve directing agent.

[0018] The preparation method of the application, the molar ratio of each component of the Y molecular sieve directing agent is (6-8) Na2O: Al2O3: (7-12) SiO2: (206-321) H2O.

[0019] The preparation method of the application, preferably, the molar ratio of each component of the Y molecular sieve directing agent is (6.5-7.5) Na2O: Al2O3: (9-11) SiO2: (220-300) H2O.

[0020] The preparation method of the application, in the sodium metaaluminate solution A, the content of Al2O3 is 4-8wt%, preferably 5-7wt%, the content of Na2O is 20-30wt%, preferably 25-30wt%.

[0021] The preparation method of the application, the content of SiO2 in the water glass solution is 20-40wt%, preferably 25-30wt% in terms of SiO2.

[0022] The preparation method of the application, in the preparation of the Y molecular sieve directing agent, the aging temperature is 20-60℃, preferably 25-40℃, and the time is 10-24h, preferably 12-24h.

[0023] The preparation method of the application, in step (2), the content of Al2O3 in the aluminum sulfate solution is 2-6wt%, preferably 3-5wt%.

[0024] The preparation method of the application, in step (2), in the sodium metaaluminate solution B, the content of Al2O3 is 5-15wt%, preferably 8-12wt%, and the content of Na2O is 5-20wt%, preferably 8-15wt%.

[0025] In the preparation method, in step (2), the organic matter comprises at least one of hydroxypropyl methyl cellulose, PEG2000, PEG200 and CTAB.

[0026] In the preparation method, in step (2), the water glass solution has a content of SiO2 of 20-40wt%, preferably 25-30wt% in terms of SiO2.

[0027] In the preparation method, in step (2), the crystallization temperature is 90-100°C, preferably 95-100°C, and the time is 24-48h.

[0028] In the preparation method, in step (3), the treatment temperature is 500-800°C, preferably 600-700°C, and the time is 0.5-2.5h, preferably 1-1.5h.

[0029] In the preparation method, in step (4), the content of ammonium sulfate in the mixed solution is 10-20wt%, preferably 10-15wt%.

[0030] In the preparation method, in step (4), the content of citric acid in the mixed solution is 10-20wt%, preferably 10-15wt%.

[0031] In the preparation method, in step (4), the treatment time is 0.5-2h, preferably 0.5-1h.

[0032] In the preparation method, in step (5), the addition amount of amorphous phosphorus aluminum is 10-20wt%, preferably 15-18wt%.

[0033] In the preparation method, in step (5), the addition amount of phosphomolybdic acid is 1-5wt%, preferably 2-4wt%.

[0034] In the preparation method, in step (5), the addition amount of macroporous alumina binder is 15-20wt%, preferably 17-18wt%.

[0035] The application further provides a catalyst carrier for producing more light naphtha and heavy naphtha in hydrocracking, wherein the specific surface area of the catalyst carrier is 550-680m 2 / g, the pore volume is 0.4-0.62mL / g, and the pore size distribution is 4-25nm.

[0036] The preparation method constructs Y / La2O3 / PMo heteropoly acid / KIT-6 microporous-mesoporous composite oxide for preparing a hydrocracking carrier, and the obtained carrier has a surface area of 550-680m2 / g, with a pore volume of 0.4 to 0.62 mL / g and a pore size distribution of 4 to 25 nm, increases the mesopore size and infrared acidity of the support, thereby improving the selective cracking performance of the support for distillate oils and increasing the yield of light naphtha and heavy naphtha. Detailed Implementation

[0037] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description. Unless otherwise specified, the raw materials used in the following embodiments and comparative examples are all commercially available.

[0038] Example 1

[0039] (1) Synthesis of Y molecular sieve directing agent: 87g sodium aluminate solution A (Al2O3 content is 4wt%, Na2O content is 20wt%) and 120g water glass solution (SiO2 content is 20wt%) were added to 35g deionized water in sequence and aged at 20℃ for 24h to obtain Y molecular sieve directing agent. The molar ratio of each component in Y molecular sieve directing agent is 8Na2O:Al2O3:12SiO2:321H2O.

[0040] (2) According to the feeding mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdenum heteropolyacid: H2O = 1:0.01:0.1:0.5, KIT-6 molecular sieve was spray-adsorbed with a complex aqueous solution of phosphomolybdenum heteropolyacid containing lanthanum nitrate. After drying and calcination, La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide was obtained.

[0041] (3) Add 5g of La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, 5g of Y molecular sieve directing agent, 80g of aluminum sulfate solution (Al2O3 content is 2wt%), 80g of sodium aluminate solution B (Al2O3 content is 5wt%, Na2O content is 5wt%) and 2g of PEG2000 to 90g of water glass solution (SiO2 content is 20wt%), stir evenly, then add 5g of deionized water and mix evenly to prepare a reaction mixture of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve. Crystallize at 95℃ for 24h to obtain a slurry of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide. After solid-liquid separation, Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is obtained.

[0042] (4) The Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide obtained in step (3) is treated with water vapor at 800℃ for 0.5 hours.

[0043] (5) The steam-treated Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide was treated in a mixed solution of 10wt% ammonium sulfate and 10wt% citric acid for 2 hours to obtain a slurry.

[0044] (6) Add 20wt% amorphous aluminum phosphide, 1wt% phosphomolybdic heteropoly acid powder and 20wt% macroporous alumina binder to the slurry in step (5), and after kneading, rolling and extruding, obtain a catalyst support containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide.

[0045] Example 2

[0046] (1) Synthesis of Y molecular sieve directing agent: 77g sodium aluminate solution A (Al2O3 content is 6wt%, Na2O content is 25wt%) and 100g water glass solution (SiO2 content is 30wt%) were added to 65g deionized water in sequence and aged at 30℃ for 18h to obtain Y molecular sieve directing agent. The molar ratio of each component in Y molecular sieve directing agent is 7Na2O:Al2O3:7SiO2:242H2O.

[0047] (2) According to the feeding mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdenum heteropoly acid: H2O = 1:0.06:0.13:1, KIT-6 molecular sieve was spray-adsorbed with a complex aqueous solution of phosphomolybdenum heteropoly acid containing lanthanum nitrate. After drying and calcination, La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide was obtained.

[0048] (3) Add 10g of La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, 10g of Y molecular sieve directing agent, 65g of aluminum sulfate solution (3wt% Al2O3 content), 65g of sodium aluminate solution B (10wt% Al2O3 content, 12.5wt% Na2O content) and 5g of PEG200 to 75g of water glass solution (27wt% SiO2 content), stir evenly, then add 50g of deionized water and mix evenly to prepare a reaction mixture of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve. Crystallize at 95℃ for 36h to obtain a slurry of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide. After solid-liquid separation, Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is obtained.

[0049] (4) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide obtained in step (3) was treated with water vapor at 650℃ for 1.5 hours.

[0050] (5) The steam-treated Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide was treated in a mixed solution of 15wt% ammonium sulfate and 15wt% citric acid for 1.25 hours to obtain a slurry.

[0051] (6) Add 15wt% amorphous aluminum phosphate, 2.5wt% phosphomolybdenum heteropoly acid powder and 18wt% macroporous alumina binder to the slurry in step (5), and after kneading, rolling and extrusion molding, a catalyst support containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is obtained.

[0052] Example 3

[0053] (1) Synthesis of Y molecular sieve directing agent: 65g sodium aluminate solution A (Al2O3 content is 8wt%, Na2O content is 30wt%) and 82g water glass solution (SiO2 content is 40wt%) were added to 100g deionized water in sequence and aged at 40℃ for 24h to obtain Y molecular sieve directing agent. The molar ratio of each component in Y molecular sieve directing agent is 6Na2O:Al2O3:11SiO2:206H2O.

[0054] (2) According to the feeding mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdenum heteropoly acid: H2O = 1: 0.12: 0.25: 2, KIT-6 molecular sieve was spray-adsorbed with a complex aqueous solution of phosphomolybdenum heteropoly acid containing lanthanum nitrate. After drying and calcination, La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide was obtained.

[0055] (3) 15g of La2O3 / PMo heteropoly acid / KIT-6 mesoporous molecular sieve oxide, 15g of Y molecular sieve directing agent, 70g of aluminum sulfate solution (Al2O3 content is 6wt%), 40g of sodium aluminate solution B (Al2O3 content is 15wt%, Na2O content is 20wt%) and 7g of CATB obtained in step (2) are added to 63g of water glass solution (SiO2 content is 40wt%), stirred evenly, and then 82g of deionized water is added and mixed evenly to prepare a reaction mixture of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve. The mixture is crystallized at 100℃ for 48h to obtain a slurry of Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide. After solid-liquid separation, Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is obtained.

[0056] (4) The Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide obtained in step (3) is treated with water vapor at 800℃ for 0.5 hours.

[0057] (5) The steam-treated Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide was treated in a mixed solution of 20wt% ammonium sulfate and 20wt% citric acid for 2 hours to obtain a slurry.

[0058] (6) Add 10wt% amorphous aluminum phosphide, 5wt% phosphomolybdenum heteropoly acid powder and 15wt% macroporous alumina binder to the slurry in step (5), and after mixing, rolling and extruding, obtain a catalyst support containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide.

[0059] Comparative Example 1

[0060] The difference from Example 3 is that no La2O3 / PMo heteropolyacid / KIT-6 molecular sieve oxide was added.

[0061] (1) Synthesis of Y molecular sieve directing agent: 65g sodium aluminate solution A (Al2O3 content is 8wt%, Na2O content is 30wt%) and 82g water glass solution (SiO2 content is 40wt%) were added to 100g deionized water in sequence and aged at 40℃ for 24h to obtain Y molecular sieve directing agent. The molar ratio of each component in Y molecular sieve directing agent is 6Na2O:Al2O3:11SiO2:206H2O.

[0062] (2) 15g of Y molecular sieve directing agent, 70g of aluminum sulfate solution (Al2O3 content is 6wt%), 40g of sodium aluminate solution B (Al2O3 content is 15wt%, Na2O content is 20wt%) and 7g of CATB were added to 63g of water glass solution (SiO2 content is 40wt%), stirred evenly, and then 82g of deionized water was added to prepare a reaction mixture for synthesizing Y. The mixture was crystallized at 100℃ for 48h to obtain a slurry of Y molecular sieve. After solid-liquid separation, Y molecular sieve was obtained.

[0063] (3) The Y molecular sieve obtained in step (2) is treated with water vapor at 800℃ for 0.5 hours.

[0064] (4) The Y molecular sieve after steam treatment was treated in a mixed solution of 20wt% ammonium sulfate and 20wt% citric acid for 2 hours to obtain a slurry.

[0065] (5) Add 10wt% amorphous aluminum phosphide, 5wt% phosphomolybdic heteropoly acid powder and 15wt% macroporous alumina binder to the slurry in step (4), and after mixing, rolling and extruding, obtain a catalyst support containing Y molecular sieve.

[0066] Comparative Example 2

[0067] The difference from Example 3 is that Beta zeolite and La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve were co-assembled to obtain Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve.

[0068] (1) Synthesis of Y molecular sieve directing agent: 65g sodium aluminate solution A (Al2O3 content is 8wt%, Na2O content is 30wt%) and 82g water glass solution (SiO2 content is 40wt%) were added to 100g deionized water in sequence and aged at 40℃ for 24h to obtain Y molecular sieve directing agent. The molar ratio of each component in Y molecular sieve directing agent is 6Na2O:Al2O3:11SiO2:206H2O.

[0069] (2) Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve was prepared using the preparation method of Example 1 of CN106311319A: 1.9g NaOH and 7.6g NaAlO2 were added to 295g TEAOH solution in sequence and stirred vigorously to mix evenly. Then, 215g TEOS was slowly added and stirred at room temperature for 4h. The mixture was then transferred to a self-pressurized reactor and crystallized at 120℃ for 24h to obtain Beta zeolite seed solution. 2g of P123 was added to 80g of 1mol / L HCl solution, followed by 30g of n-butanol. After stirring for 4 hours, 50g of TEOS was added, and stirring was continued at 40℃ for 2 hours. Then, 80g of the previously prepared Beta zeolite seed solution was added, followed by 5g of La2O3 / PMo heteropolyacid / KIT-6 molecular sieve. The mixture was stirred at 40℃ for 24 hours, then transferred to a self-pressurized reactor and crystallized at 100℃ for 24 hours. After filtration, washing, drying, and calcination at 550℃, the Beta / La2O3 / PMo heteropolyacid / KIT-6 micro-mesoporous composite molecular sieve was finally obtained.

[0070] (3) 15g of Beta / La2O3 / PMo heteropoly acid / KIT-6 micro-mesoporous composite molecular sieve, 15g of Y molecular sieve directing agent, 70g of aluminum sulfate solution (Al2O3 content is 6wt%), 40g of sodium aluminate solution B (Al2O3 content is 15wt%, Na2O content is 20wt%) and 7g of CATB obtained in step (2) were added to 63g of water glass solution (SiO2 content is 40wt%), stirred evenly, and then 82g of deionized water was added to prepare a reaction mixture for synthesizing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve. The mixture was crystallized at 100℃ for 48h to obtain a slurry of Y / Beta / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide. After solid-liquid separation, Y / Beta / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide was obtained.

[0071] (4) The Y / Beta / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide obtained in step (3) was treated with water vapor at 800℃ for 0.5 hours.

[0072] (5) The steam-treated Y / Beta / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide was treated in a mixed solution of 20wt% ammonium sulfate and 20wt% citric acid for 2 hours to obtain a slurry.

[0073] (6) Add 10wt% amorphous aluminum phosphate, 5wt% phosphomolybdenum heteropoly acid powder and 15wt% macroporous alumina binder to the slurry in step (5), and after kneading, rolling and extrusion molding, a catalyst support containing Y / Beta / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide is obtained.

[0074] Table 1 Properties of Molecular Sieves Composite Oxides

[0075]

[0076] Table 2. Carrier Properties

[0077]

[0078]

[0079] Evaluation Example 1

[0080] The performance of the catalyst support was evaluated using the feedstock oils listed in Table 3. The reaction conditions and evaluation results are shown in Table 4.

[0081] Table 3 Properties of Feed Oil

[0082] Item High aromatics distillate oil Density, g / cm 3 (20°C) 0.855 Distillation range, °C 280～500 Nitrogen, pg / g 901 Sulfur, pg / g 1220 Mass spectral composition Paraffins, wt% 36.1 Naphthenes, wt% 23.8 Aromatics, wt% 40.1 Monocyclic aromatics 18.0 Bicyclic aromatics 19.2 Tricyclic aromatics 2.9

[0083] Table 4 Reaction performance of hydrocracking catalysts

[0084]

[0085]

[0086] As can be seen from the results in Table 4, the preparation method of the present invention improves the mesopore size distribution, enhances the selective cracking performance of distillate oil, and increases the yield of light naphtha and heavy naphtha by constructing a catalyst support for hydrocracking containing Y molecular sieve and La2O3 / PMo heteropoly acid / KIT-6 molecular sieve.

[0087] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a catalyst support for hydrocracking that yields both light and heavy naphtha, characterized in that, The catalyst support contains a mesoporous composite oxide of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve, and the preparation method includes the following steps: (1) KIT-6 molecular sieve was spray-adsorbed with an aqueous solution of phosphomolybdic heteropolyacid containing lanthanum nitrate, and then dried and calcined to obtain La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide; (2) The La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide, Y molecular sieve directing agent, aluminum sulfate solution, sodium aluminate solution B, and organic matter obtained in step (1) are added to a water glass solution, stirred evenly, and then deionized water is added. After mixing evenly and crystallizing, a slurry of Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide is obtained. The mass ratio of La2O3 / PMo heteropolyacid / KIT-6 mesoporous molecular sieve oxide: Y molecular sieve directing agent: Al2O3: Na2O: SiO2: organic matter: H2O is (0.8 ~ 1.5): (0.09 ~ 0.15): 1: (0.08 ~ 0.96): (2.4 ~ 3.2): (0.3 ~ 0.7): (13 ~ 41); After solid-liquid separation, the slurry yields a Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide. (3) The Y / La2O3 / PMo heteropolyacid / KIT-6 molecular sieve mesoporous composite oxide was treated under water vapor conditions; (4) The steam-treated Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide was treated in a mixed solution of ammonium sulfate and citric acid to obtain a slurry; (5) Add amorphous aluminum phosphide, phosphomolybdenum heteropoly acid and macroporous alumina binder to the slurry in step (4), and after kneading, rolling and extruding, obtain a catalyst support containing Y / La2O3 / PMo heteropoly acid / KIT-6 molecular sieve mesoporous composite oxide. In step (2), the preparation method of the Y molecular sieve directing agent includes: Sodium aluminate solution A and water glass solution were added to deionized water and aged to obtain Y molecular sieve directing agent; In step (2), the organic compound includes at least one of hydroxypropyl methylcellulose, PEG2000, PEG200, and CTAB.

2. The preparation method according to claim 1, characterized in that, In step (1), the mass ratio of KIT-6 molecular sieve: lanthanum nitrate: phosphomolybdic heteropoly acid: water is 1: (0.01~0.12): (0.1~0.25): (0.5~2).

3. The preparation method according to claim 1 or 2, characterized in that, The molar ratio of each component in the Y molecular sieve directing agent is (6~8) Na2O:Al2O3:(7~12)SiO2:(206~321)H2O.

4. The preparation method according to claim 1, characterized in that, In the sodium aluminate solution A, the content of Al2O3 is 4-8 wt%, and the content of Na2O is 20-30 wt%. The water glass solution contains 20-40 wt% SiO2.

5. The preparation method according to claim 1, characterized in that, In step (2), the content of Al2O3 in the aluminum sulfate solution is 2-6 wt%. In the sodium aluminate solution B, the content of Al2O3 is 5-15 wt%, and the content of Na2O is 5-20 wt%.

6. The preparation method according to claim 1, characterized in that, In step (2), the water glass solution contains 20-40 wt% SiO2.

7. The preparation method according to claim 1, characterized in that, In step (4), the content of ammonium sulfate in the mixed solution is 10~20wt%, and the content of citric acid is 10~20wt%.

8. The preparation method according to claim 1, characterized in that, In step (5), the amount of amorphous aluminum phosphate added is 10~20wt%; The amount of the phosphomolybdic acid added is 1~5 wt%; The amount of the macroporous alumina binder added is 15~20wt%.

9. A catalyst support for hydrocracking to produce both light naphtha and heavy naphtha, characterized in that, The carrier, prepared by any one of claims 1-8, has a specific surface area of ​​550-680 m². 2 / g, pore volume is 0.4~0.62mL / g, pore size distribution is 4~25nm.

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